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Lecture 39 PDF

1) The document summarizes a lecture on nucleophilic aromatic substitution and elimination reactions. 2) It discusses the mechanisms of E1 and E2 elimination reactions, including factors that influence their rates such as solvent, leaving group ability, and substrate structure. 3) The Hofmann elimination and Cope elimination are specialized types of E2 reactions that are discussed in detail.

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Rachit Shah
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102 views20 pages

Lecture 39 PDF

1) The document summarizes a lecture on nucleophilic aromatic substitution and elimination reactions. 2) It discusses the mechanisms of E1 and E2 elimination reactions, including factors that influence their rates such as solvent, leaving group ability, and substrate structure. 3) The Hofmann elimination and Cope elimination are specialized types of E2 reactions that are discussed in detail.

Uploaded by

Rachit Shah
Copyright
© © All Rights Reserved
We take content rights seriously. If you suspect this is your content, claim it here.
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Download as PDF, TXT or read online on Scribd
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BITS Pilani

Pilani Campus

CHEM F111 : General Chemistry


II-Semester: AY 2018-19
Lecture 39 (26-04-2019)
BITS Pilani, Pilani Campus
Summary of Lecture 37

A negatively charged
Nucleophilic Aromatic Substitution (SNAr)
nucleophile is always a
stronger nucleophile
Nucleophilic Substitution Reactions: than its conjugate acid.
Role of leaving group, nucleophile and solvents
 Steric hindrance decreases nucleophilicity but not basicity of a charged species.
 All SN2 reactions results in inversion of configuration at a stereogenic center.
 All SN1 proceed through Carbocations that are trigonal planar.
 Carbocations can rearrange to form a more stable carbocation.
 Best solvents for SN2 rxs are Polar Aprotic solvents.
 Best solvents for SN1 rxs are Polar protic solvents
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Elimination Reactions
Alkyl halide + strong base & heat Alcohol + strong acid & heat

The b-hydrogen is H
a-carbon
attached to the b-carbon.
C C
b-carbon Cl The functional group is
attached to the a-carbon.
Since the b-hydrogen is lost this reaction is called a b-elimination
The stability of an alkene increases as the number of R
groups bonded to the double bond carbons increases.

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Mechanisms of Elimination
There are two mechanisms of elimination E2 and E1
• E2 mechanism - bimolecular elimination
• E1 mechanism - unimolecular elimination
Both the mechanisms differ in the timing of bond cleavage
and bond formation
E2 reactions are generally run with strong, negatively charged
bases like -OH and -OR.
The reaction exhibits second-order kinetics, and both the
alkyl halide and the base appear in the rate equation i.e.
rate = k[(CH3)3CBr][-OH]
The reaction is concerted—all bonds are broken and formed
in a single step.
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E2-Elimination Reaction
Because the bond to the leaving group is partially broken in
the transition state, the better the leaving group the faster
the E2 reaction.
Increasing leaving group ability
Increasing rate of E2 rexn.

The SN2 and E2 mechanisms differ in how the R group affects


the reaction rate. As the number of R groups on the carbon
with the leaving group increases, the rate of the E2 reaction
increases.

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E2-Elimination Reaction
The increase in E2 reaction rate with increasing alkyl
substitution can be rationalized in terms of transition state
stability & steric hindrance for SN2
In the transition state, the double bond is partially formed.
Thus, increasing the stability of the double bond with alkyl
substituents stabilizes the transition state.

SN2 is too
hindered
The double bond is
CH3O-
X partially formed

H CH3 H CH3
CH3 E2
H + CH3OH + Br-
H Br H CH3
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Regioslectivity & Stereochemistry of E2 Rexn
If more than one elimination product is possible, the most-
substituted alkene is the major product (most stable)- Zaitsev’s
(Saytzeff) rule CH - CH3
3 CH3O CH3
CH2CH3 H2C + H3C
H3C
E2 CH2CH3 CHCH3
Br
Minor Major

E2-elimination occurs most often in the anti-periplanar geometry.


This arrangement allows the molecule to react in the lower energy
staggered conformation, and allows the incoming base and leaving
group to be further away from each other.

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Stereochemistry of E2 Rexn
Z or E ?

Major Product Minor Product

-OH

E2 is both stereoselective and stereospecific.


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Stereochemistry of E2 Rexn

What about (2R, 3R) and (2R, 3S) isomers?

major product

cis- reacts faster than trans- as activation energy for cis- is lower.
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Formation of Hofmann Product
Bulky bases abstract the least hindered H+ to give least substituted
alkene as major product.

Some bulky bases:


They are strong base,
poor nucelophile.
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E1-Elimination reaction
 An E1 reaction exhibits first-order kinetics:
rate = k[(CH3)3CI]
The E1 reaction proceed via a two-step mechanism.
The bond to the leaving group breaks first before the  bond
is formed.
The slow step is unimolecular, involving only the alkyl halide.
Intermediate carbocation is formed.

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Free Energy Diagram of E1 Reactions

The rate of an E1 reaction increases as the number of R groups on


the carbon with the leaving
group increases.
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E1-Elimination reaction

• These reactions proceed under neutral conditions where a


polar solvent helps to stabilize the carbocation intermediate.
• This polar solvent also acts as a weak base and removes a
proton in the fast step.
• These types of reactions are referred to as solvolysis reactions.
• Tertiary substrates go by E1 in polar solvents, with little or no
base present!
• Typical polar solvents are water, ethanol, methanol and acetic
acid
• E1 reactions also occur in a low concentration of base (i.e.
0.01M NaOH).

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E1-Elimination reaction
E1 reactions are regioselective, favoring formation of the more
substituted, more stable alkene. E1 reactions follow the Zaitsev’s
rule.

Rearrangements occur in E1 reactions.


E1 reactions do not require an anti coplanar orientation of H and
X.
Diastereomers give the same products with E1 reactions, including
cis- and trans products.
E1 reactions usually give the thermodynamically most stable
product as the major product.
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Hofmann Elimination
 Hofmann elimination, also known as exhaustive methylation, is
a process where an amine is reacted to create a tertiary amine
and an alkene by treatment with excess methyl iodide/primary
halide followed by treatment with silver oxide, water, and
heat.

Ag2O

A Hofmann elimination is an E2 reaction


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Hofmann Elimination
Heating quaternary ammonium hydroxide produces the least
substituted alkene.
A quaternary ammonium salt is a good leaving group as neutral
amine.
The leaving group of a quaternary ammonium ion has about the
same leaving tendency as a protonated amino group.
N,N,N-trimethyl-N-(2-butyl) ammonium hydroxide

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Hofmann Elimination

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Cope Elimination
The Cope elimination of N-oxides, which can easily be prepared in situ
from tertiary amines with an oxidant such as peracid is a syn periplanar
elimination in which six electrons move in a five-membered ring
according to a concerted, thermally-induced mechanism to yield an
alkene and a hydroxylamine in aprotic solvents.

The sterically demanding amine oxide function reacts preferentially with


the more easily accessible hydrogens, and often gives good selectivity
favoring the less-substituted alkene. Thus, for simple alkenes, the
reaction follows the Hofmann Rule
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Cope Elimination

mCPBA

Heat

mCPBA

Heat

Preferred

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Comparison of E1 and E2 Elimination

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